The kinetics and mechanism of the low temperature post-polymerization of allylamine in the presence of phosphoric acid

Kreindel, M.Ya.; Andreyeva, L.I.; Kaplan, A.M.; Голубев, В. Б.; Masterova, M.N.; Zubov, V.P.; Polak, L.S.; Kabanov, V.A.

doi:10.1016/0032-3950(76)90181-7

Cited by 7 publications

(8 citation statements)

References 5 publications

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“…The schematic representation of cryogels formation via cryopolymerization technique is shown in Figure . To enhance the activity of allylamine and increase the yield of the gel fraction of copolymerized AMPS and AA, allylamine was converted to a phosphate complex by mixing with phosphoric acid. , Placing the monomeric solution at subzero temperatures initiates the growth of ice crystals, which occurs with radical polymerization of selected monomers, and the cross-linking of polymer chains to form branched macromers in unfrozen liquid microphase . The size of the formed ice crystals depends on the temperature in the cryobath.…”

Section: Resultsmentioning

confidence: 99%

Experimental and Modeling Studies of Sr²⁺ and Cs⁺ Sorption on Cryogels and Comparison to Commercial Adsorbents

Baimenov

Montagnaro

Inglezakis

et al. 2022

Ind. Eng. Chem. Res.

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In this work, two cryogels with the key monomers methacrylic acid and 2-acrylamido-2-methyl-1-propansulfonic acid (named AAC and SAC, respectively) with various functional groups were used as adsorbents for the removal of cesium and strontium ions from aqueous solutions. Kinetics, equilibrium, and column studies were carried out including experiments in different water matrices (ultrapure, tap, and river water) and comparison to commercial adsorbents. AAC reached sorption capacity of 362 mg g −1 for Cs + and 209 mg g −1 for Sr 2+ , whereas SAC polymer showed maximum removal capacities of 259 and 211 mg g −1 for Cs + and Sr 2+ , respectively. The five cycles of adsorption/desorption experiments showed a maximum of 8% loss of effectiveness for both cryogels. Batch kinetics adsorption data were modeled by using a rigorous diffusional model coupled to a novel fractal-like expression for variable surface diffusivity. The model revealed that the surface diffusivity dependence on time is nonmonotonic, with the occurrence of a maximum. Also, both fluid film and intraparticle transport resistances were shown to be important, with the internal one being more influential. The cryogels and two commercial materials (ion-exchange resin and zeolite) were tested for the removal of Cs + and Sr 2+ in ultrapure, tap, and river water; the results showed that the cryogels exhibit competitive effectiveness.

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Section: Resultsmentioning

confidence: 99%

Experimental and Modeling Studies of Sr²⁺ and Cs⁺ Sorption on Cryogels and Comparison to Commercial Adsorbents

Baimenov

Montagnaro

Inglezakis

et al. 2022

Ind. Eng. Chem. Res.

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“…The methacrylic acid co-polymerized with allylamine gives a low yield of the gel fraction due to the low activity of allylamine [ 29 ]. One way to enhance the activity of allylamine is to convert it to a phosphate complex [ 30 , 31 ], which can be done via mixing of allylamine with phosphoric acid. Simultaneously to radical polymerization of selected monomers and the crosslinking of polymer chains takes place to form branched macromers, ice crystals grow, which displace all components of the reaction mixture into an unfrozen liquid microphase [ 29 ].…”

Section: Resultsmentioning

confidence: 99%

Removal of Cd2+ from Water by Use of Super-Macroporous Cryogels and Comparison to Commercial Adsorbents

et al. 2020

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In this study amphoteric cryogels were synthesized by the use of free-radical co-polymerization of acrylate-based precursors (methacrylic acid and 2-acrylamido-2-methyl-1-propansulfonic acid) with allylamine at different ratios. The physico-chemical characteristics of the cryogels were examined using SEM/EDX, FT-IR, XPS and zeta potential measurements. The cryogels were tested toward Cd2+ removal from aqueous solutions at various pH and initial concentrations. Equilibrium studies revealed a maximum sorption capacity in the range of 132–249 mg/g. Leaching experiments indicated the stability of Cd2+ in the cryogel structure. Based on kinetics, equilibrium and characterization results, possible removal mechanisms are proposed, indicating a combination of ion exchange and complexation of Cd2+ with the cryogels’ surface functional groups. The cryogels were compared to commercially available adsorbents (zeolite Y and cation exchange resin) for the removal of Cd2+ from various water matrices (ultrapure water, tap water and river water) and the results showed that, under the experimental conditions used, the cryogels can be more effective adsorbents.

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“…It is possible to state that in none of the polymerization systems consid- 5 Experimental data will be published in full. 6 The reasons for the activation of allyl radicals of chain transfer are not yet absolutely clear for the case of polymerization of both allyl and diallyl monomers.…”

Section: Resultsmentioning

confidence: 99%

“…5 Having studied the polymerization process kinetics, we established that the bimolecular mechanism controls chain termination. Based on this finding, we can make the fundamental conclusion that degradative chain transfer to monomer, characteristic for allyl monomers, does not occur in the given system [16,30].…”

Section: Resultsmentioning

confidence: 99%

“…Taking into account the aforesaid, we studied three reaction systems (I-III) simulating the elementary reactions of chain propagation and chain transfer to the monomer upon polymerization of compound 1, its protonated form, viz., diallylmethylammonium (5), and the diallyldimethylammonium cation (6) (Scheme 1). System I was used to consider the elementary reactions occurring upon STRUCTURE 1.…”

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Radical polymerization of diallylamine compounds: From quantum chemical modeling to controllable synthesis of high‐molecular‐weight polymers

Timofeeva

Vasilieva

Kleshcheva

et al. 2002

Int J of Quantum Chemistry

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ABSTRACT:We investigated the possibility to obtain high-molecular-weight (HMW) polymers from the monomers of the diallylamine (DAA) series using quantum chemical and experimental methods. Such monomers are known to polymerize into oligomeric products due to the reaction of the degradative chain transfer to the monomer. We studied potential energy profiles of the chain propagation and competing chain transfer reactions, viz., the free radical double bond addition and ␣-hydrogen radical abstraction, respectively, for a number of polymerization processes. Calculations were carried in the framework of the polarized continuum solvent model utilizing the procedure based on the semiempirical MNDO-PM3 background. It was found that the necessary condition for decreasing competitiveness of the chain transfer to the monomer is the availability of monomer molecules in only protonated form in the polymerizing system. Using these results, we developed the strategy for obtaining HMW polymers based on said monomers. We synthesized a monomer system (the equimolar salt of N,N-diallyl-N-methylamine and trifluoroacetic acid) that fully corresponds to such requirements. Novel HMW polymers were then synthesized by radical polymerization of this salt at soft conditions. We established that chain termination is controlled by the bimolecular mechanism. We showed that the degradative chain transfer transforms into the effective chain transfer. The mechanisms of the observed phenomena are discussed.

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The kinetics and mechanism of the low temperature post-polymerization of allylamine in the presence of phosphoric acid

Cited by 7 publications

References 5 publications

Experimental and Modeling Studies of Sr²⁺ and Cs⁺ Sorption on Cryogels and Comparison to Commercial Adsorbents

Experimental and Modeling Studies of Sr²⁺ and Cs⁺ Sorption on Cryogels and Comparison to Commercial Adsorbents

Removal of Cd2+ from Water by Use of Super-Macroporous Cryogels and Comparison to Commercial Adsorbents

Radical polymerization of diallylamine compounds: From quantum chemical modeling to controllable synthesis of high‐molecular‐weight polymers

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The kinetics and mechanism of the low temperature post-polymerization of allylamine in the presence of phosphoric acid

Cited by 7 publications

References 5 publications

Experimental and Modeling Studies of Sr2+ and Cs+ Sorption on Cryogels and Comparison to Commercial Adsorbents

Experimental and Modeling Studies of Sr2+ and Cs+ Sorption on Cryogels and Comparison to Commercial Adsorbents

Removal of Cd2+ from Water by Use of Super-Macroporous Cryogels and Comparison to Commercial Adsorbents

Radical polymerization of diallylamine compounds: From quantum chemical modeling to controllable synthesis of high‐molecular‐weight polymers

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Experimental and Modeling Studies of Sr²⁺ and Cs⁺ Sorption on Cryogels and Comparison to Commercial Adsorbents

Experimental and Modeling Studies of Sr²⁺ and Cs⁺ Sorption on Cryogels and Comparison to Commercial Adsorbents